原位^(57)Fe穆斯堡尔光谱技术及其在Ni-Fe基析氧反应电催化剂中的应用  

In-Situ/Operando ^(57)Fe M?ssbauer Spectroscopic Technique and Its Applications in NiFe-based Electrocatalysts for Oxygen Evolution Reaction

作　　者：Jafar Hussain Shah 谢起贤 匡智崇 格日乐[1] 周雯慧 刘朵绒 Alexandre I.Rykov 李旭宁[1] 罗景山 王军虎[1] Jafar Hussain Shah;Qi-Xian Xie;Zhi-Chong Kuang;Ri-Le Ge;Wen-Hui Zhou;Duo-Rong Liu;Alexandre IRykov;Xu-Ning Li;Jing-Shan Luo;Jun-Hu Wang(Center for Advanced Mossbauer Spectroscopy,Mossbauer Effect Data Center,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,Liaoning,China;Institute of Photoelectronic Thin Film Devices and Technology,Key Laboratory of Photoelectronic Thin Film Devices and Technology of Tianjin,Ministry of Education Engineering Research Center of Thin Film Photoelectronic Technology,Renewable Energy Conversion and Storage Center,Nankai University,Tianjin 300350,China)

机构地区：[1]中国科学院大连化学物理研究所,大连116023 [2]南开大学,天津300350

出　　处：《电化学》2022年第3期48-78,共31页Journal of Electrochemistry

基　　金：financially supported by the National Natural Science Foundation of China (No.: 21961142006);the International Partnership Program of Chinese Academy of Sciences (No.: 121421KYSB20170020)。

摘　　要：近年来,析氧反应(oxygen evolution reaction)中针对高效且具有成本效益的电催化剂开发一直是构筑有效利用可再生能源存储系统和水分解生产清洁氢能燃料的重大障碍。OER过程涉及四电子、四质子耦合并形成氧-氧(O-O)键,因此动力学上进程缓慢。为提升其在水分解产氢及二氧化碳还原反应中的应用,需要开发高效催化剂,降低OER过电位,以减轻能量转换过程中固有的能量损失。研究表明,IrO;和RuO;具有较低析氧过电位,但储量低、价格昂贵,大大限制了其在析氧反应中的大规模应用。而Ni-Fe基析氧催化剂在碱性水分解反应中展现了优异的性能,其在水分解过程中的催化机制仍有待进一步研究。为了解决Ni-Fe基催化剂在析氧反应过程中反应位点及催化反应机制等关键问题,迫切需要更先进的原位技术来准确表征,原位追踪催化剂形态变化与电解质/电极之间的界面相互作用的影响。光谱与电化学结合的原位技术可以监测析氧反应过程催化剂自身的变化。目前,已有大量原位光谱技术与电化学进行结合,揭示Ni-Fe基催化剂在OER过程中的反应机理及活性位点,包括原位表面增强拉曼光谱、原位同步辐射X射线吸收光谱、原位紫外-可见光谱、原位扫描电化学显微镜及原位穆斯堡尔光谱等。其中,原位拉曼技术可以观察Ni-Fe催化剂的振动,可以在电解液中施加测试电压条件下监测电化学反应过程中的中间体,从而提供实时反应信息,有助于追踪电化学驱动反应是如何发生的。原位同步辐射技术可以研究OER过程中Ni-Fe催化剂材料的电子结构和局部几何结构的信息,但目前的研究中更多的是探究Ni的价态变化,对Fe的研究信息较少。原位紫外-可见光谱也主要是针对Ni(OH);的变化展开研究,逐渐提高施加电位,Ni(OH);会向着Ni OOH逐渐变化,紫外-可见技术可以追踪Ni-Fe基电催化剂中的金属氧�The development of highly efficient and cost-effective electrocatalysts for the sluggish oxygen evolution reaction(OER) remains a significant barrier to establish effective utilization of renewable energy storage systems and water splitting to produce clean fuel. The current status of the research in developing OER catalysts shows that NiFe-based oxygen evolution catalysts(OECs) have been proven as excellent and remarkable candidates for this purpose. But it is critically important to understand the factors that influence their activity and underlying mechanism for the development of state-of-the-art OER catalysts. Therefore, the development of in-situ/operando characterizations is urgently required to detect key intermediates along with active sites and phases responsible for OER.;Fe M?ssbauer spectroscopy is one of the appropriate and suitable techniques for determining the phase structure of catalysts under their electrochemical working conditions, identifying the active sites, clarifying the catalytic mechanisms, and determining the relationship between catalytic activity and the coordination structure of catalysts. In this tutorial review, we have discussed the current status of research on NiFe-based catalysts with particular attention to introduce in detail the knowhow about the development and utilization of in-situ/operando;Fe M?ssbauer-electrochemical spectroscopy for the study of OER mechanism.A brief overview using NiFe-(oxy)hydroxide catalysts, derived from ordered porous metal-organic framework(MOF) material NiFePBAs(Prussian blue analogues), as a typical model study case for the OER electrocatalyst and self-designed in-situ/operando;Fe M?ssbauer-electrochemical instrument, has been provided for the better understanding of readers. Moreover, using in-situ/operando;Fe M?ssbauer spectroscopy, the crucial role of Fe species during OER reaction has been explained very well.

关 键 词：析氧反应 Ni-Fe羟基氧化物电催化剂 原位电化学穆斯堡尔光谱技术 Ni-Fe普鲁士蓝类似物 关键中间物表征 

分 类 号：O643.36[理学—物理化学] O657.3[理学—化学]